CN114029090B - Preparation method of photocatalyst for removing heavy metals in sewage - Google Patents
Preparation method of photocatalyst for removing heavy metals in sewage Download PDFInfo
- Publication number
- CN114029090B CN114029090B CN202111560651.2A CN202111560651A CN114029090B CN 114029090 B CN114029090 B CN 114029090B CN 202111560651 A CN202111560651 A CN 202111560651A CN 114029090 B CN114029090 B CN 114029090B
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- CN
- China
- Prior art keywords
- bismuth
- photocatalyst
- metal oxide
- based multi
- heavy metals
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 28
- 239000010865 sewage Substances 0.000 title claims abstract description 15
- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 34
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000013299 conductive metal organic framework Substances 0.000 claims abstract description 28
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 23
- 229910052751 metal Chemical class 0.000 claims abstract description 16
- 239000002184 metal Chemical class 0.000 claims abstract description 16
- 239000002131 composite material Substances 0.000 claims abstract description 14
- 239000002243 precursor Substances 0.000 claims abstract description 14
- 239000002904 solvent Substances 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 14
- 238000004140 cleaning Methods 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 150000001621 bismuth Chemical class 0.000 claims abstract description 7
- 239000013110 organic ligand Substances 0.000 claims abstract description 7
- 150000003839 salts Chemical class 0.000 claims abstract description 7
- 238000001914 filtration Methods 0.000 claims abstract description 6
- 239000012702 metal oxide precursor Substances 0.000 claims abstract description 6
- 239000000654 additive Substances 0.000 claims abstract description 3
- 230000000996 additive effect Effects 0.000 claims abstract description 3
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 4
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 4
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 4
- 239000011609 ammonium molybdate Substances 0.000 claims description 4
- 229940010552 ammonium molybdate Drugs 0.000 claims description 4
- OWSZUKMVEBFJMZ-UHFFFAOYSA-N benzene-1,2,3,4,5,6-hexamine Chemical compound NC1=C(N)C(N)=C(N)C(N)=C1N OWSZUKMVEBFJMZ-UHFFFAOYSA-N 0.000 claims description 4
- ANUAIBBBDSEVKN-UHFFFAOYSA-N benzene-1,2,4,5-tetramine Chemical compound NC1=CC(N)=C(N)C=C1N ANUAIBBBDSEVKN-UHFFFAOYSA-N 0.000 claims description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 3
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims description 3
- IHIXIJGXTJIKRB-UHFFFAOYSA-N trisodium vanadate Chemical compound [Na+].[Na+].[Na+].[O-][V]([O-])([O-])=O IHIXIJGXTJIKRB-UHFFFAOYSA-N 0.000 claims description 3
- SATWKVZGMWCXOJ-UHFFFAOYSA-N 4-[3,5-bis(4-carboxyphenyl)phenyl]benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC(C=2C=CC(=CC=2)C(O)=O)=CC(C=2C=CC(=CC=2)C(O)=O)=C1 SATWKVZGMWCXOJ-UHFFFAOYSA-N 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- HJCNSOVRAZFJLK-UHFFFAOYSA-N C1=CC(C(=O)O)=CC=C1C1=CC2=CC([N]3)=CC=C3C=C(C=C3)NC3=CC([N]3)=CC=C3C=C1N2 Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC2=CC([N]3)=CC=C3C=C(C=C3)NC3=CC([N]3)=CC=C3C=C1N2 HJCNSOVRAZFJLK-UHFFFAOYSA-N 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 claims description 2
- 229930195725 Mannitol Natural products 0.000 claims description 2
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 2
- NVGVNJDFTHQFQR-UHFFFAOYSA-N benzene-1,2,3,4,5,6-hexathiol Chemical compound SC1=C(S)C(S)=C(S)C(S)=C1S NVGVNJDFTHQFQR-UHFFFAOYSA-N 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- RBTKNAXYKSUFRK-UHFFFAOYSA-N heliogen blue Chemical compound [Cu].[N-]1C2=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=NC([N-]1)=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=N2 RBTKNAXYKSUFRK-UHFFFAOYSA-N 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 239000000594 mannitol Substances 0.000 claims description 2
- 235000010355 mannitol Nutrition 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- PNYYBUOBTVHFDN-UHFFFAOYSA-N sodium bismuthate Chemical compound [Na+].[O-][Bi](=O)=O PNYYBUOBTVHFDN-UHFFFAOYSA-N 0.000 claims description 2
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 claims description 2
- 235000015393 sodium molybdate Nutrition 0.000 claims description 2
- 239000011684 sodium molybdate Substances 0.000 claims description 2
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- NAFSMMJPUQZBRJ-UHFFFAOYSA-N Cl.[Bi] Chemical compound Cl.[Bi] NAFSMMJPUQZBRJ-UHFFFAOYSA-N 0.000 claims 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims 1
- AZOOXWWPWARTFV-UHFFFAOYSA-N zirconium hydrochloride Chemical compound Cl.[Zr] AZOOXWWPWARTFV-UHFFFAOYSA-N 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 15
- 239000012621 metal-organic framework Substances 0.000 abstract description 6
- 239000000969 carrier Substances 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- 239000004065 semiconductor Substances 0.000 abstract description 4
- 238000013329 compounding Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 25
- 230000001699 photocatalysis Effects 0.000 description 15
- 239000003054 catalyst Substances 0.000 description 7
- 238000007146 photocatalysis Methods 0.000 description 6
- 230000009286 beneficial effect Effects 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 239000012921 cobalt-based metal-organic framework Substances 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- DKUYEPUUXLQPPX-UHFFFAOYSA-N dibismuth;molybdenum;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Mo].[Mo].[Bi+3].[Bi+3] DKUYEPUUXLQPPX-UHFFFAOYSA-N 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 238000005215 recombination Methods 0.000 description 3
- 230000006798 recombination Effects 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910000380 bismuth sulfate Inorganic materials 0.000 description 2
- ZBYYWKJVSFHYJL-UHFFFAOYSA-L cobalt(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Co+2].CC([O-])=O.CC([O-])=O ZBYYWKJVSFHYJL-UHFFFAOYSA-L 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- BEQZMQXCOWIHRY-UHFFFAOYSA-H dibismuth;trisulfate Chemical compound [Bi+3].[Bi+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O BEQZMQXCOWIHRY-UHFFFAOYSA-H 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 description 2
- YMKHJSXMVZVZNU-UHFFFAOYSA-N manganese(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YMKHJSXMVZVZNU-UHFFFAOYSA-N 0.000 description 2
- 239000013239 manganese-based metal-organic framework Substances 0.000 description 2
- 239000013099 nickel-based metal-organic framework Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 241001198704 Aurivillius Species 0.000 description 1
- 239000013255 MILs Substances 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012924 metal-organic framework composite Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000002127 nanobelt Substances 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 230000001443 photoexcitation Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2213—At least two complexing oxygen atoms present in an at least bidentate or bridging ligand
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/34—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of chromium, molybdenum or tungsten
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/56—Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/70—Complexes comprising metals of Group VII (VIIB) as the central metal
- B01J2531/72—Manganese
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/845—Cobalt
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/847—Nickel
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/22—Chromium or chromium compounds, e.g. chromates
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a preparation method of a photocatalyst for removing heavy metals in sewage, which comprises the following steps: s1: adding bismuth salt and metal salt into the solvent A, and fully stirring and dissolving to form bismuth-based multi-metal oxide precursor solution; s2: putting the bismuth-based multi-metal oxide precursor solution into a high-pressure reaction kettle, performing hydrothermal reaction for 6-48h at 120-200 ℃, filtering, and then cleaning and drying to obtain the bismuth-based multi-metal oxide; s3: adding a metal source, an organic ligand and an additive into the solvent B, and fully stirring and dissolving to form a conductive MOF precursor solution; s4: and (2) adding the bismuth-based multi-metal oxide prepared in the step (S2) into the conductive MOF precursor solution, stirring to fully dissolve, then reacting for 2-48h at 25-150 ℃, filtering, cleaning and drying to obtain the bismuth-based multi-metal oxide/conductive MOF composite photocatalyst. The invention can solve the problem of poor activity of the photocatalyst formed by adopting MOF materials as carriers and compounding other semiconductor materials.
Description
Technical Field
The invention relates to the technical field of photocatalytic materials, in particular to a preparation method of a photocatalyst for removing heavy metals in sewage.
Background
Tap water used in life often contains heavy metals (such as Cr, cd, pb and the like) and causes serious threat to the health of human bodies, animals and plants. At present, the photocatalysis treatment of sewage is considered as a promising method, and bismuth-based multi-metal oxide (BiMOx) with Aurivillius lamellar characteristics has excellent physicochemical properties, unique ferroelectric properties, catalytic properties and the like, is a good visible light catalyst, and shows great advantages in photocatalysis. However, biMOx has low light quantum efficiency and is easy to compound electron and hole, and the key for improving the photocatalysis performance of the BiMOx is to regulate and control a band gap structure and inhibit the recombination of photon-generated carriers through the optimization of morphology, structure and components. The conductive Metal Organic Framework (MOF) material not only has the characteristics of the traditional MOF material such as ultrahigh specific surface area, porosity, adjustable structure and the like, but also is beneficial to the adsorption and diffusion of pollutants and products, and forms an ideal reaction platform for photocatalysis; and the conductive MOF material also has higher conductivity, thereby being beneficial to improving the photo-generated carrier separation efficiency of the photocatalyst.
Chinese patent CN 110047657a describes an MILs series MOF composite bismuth vanadate-molybdenum-doped photo-anode and a preparation method thereof, wherein the photo-current of the photo-anode is improved by the combination of bismuth vanadate doped with molybdenum and MOF material.
The Chinese patent CN 103657634A adopts graphene as a carrier to modify bismuth molybdate nano-belts, so as to obtain a novel photocatalyst with strong adsorption and high photocatalytic activity under sunlight. The inventor considers that the graphene has strong electron conduction capability and electron storage capability, can capture and conduct photoexcitation electrons, and prevents the recombination of photon-generated carriers in the semiconductor catalyst.
Zhu et al (Selective Reduction of CO) 2 by Conductive MOF Nanosheets as an Efficient Co-catalyst under Visible Light Illumination) for the first time use of conductive MOF materials for photocatalytic CO 2 The reduced cocatalyst finds out pi electrons conjugated in two dimensions and rich Ni-N4 active sites in the conductive MOF, so that the conductive MOF has high conductivity and high activity.
Zhao et al (Carbon nitride assisted 2D conductive metal-organic frameworks composite photocatalyst for efficient visible light-drive H 2 O 2 production) toC 3 N 4 The carrier is loaded with two-dimensional conductive MOF (Ni-CAT) to obtain Ni-CAT/C 3 N 4 Composite photocatalyst and pure C 3 N 4 Or Ni-CAT comparison, find Ni-CAT/C 3 N 4 The composite photocatalyst can catalyze oxygen to reduce into H under light 2 O 2 The efficiency of (2) increases exponentially. Under the irradiation of visible light, electrons generated on CN can be transferred to Ni-CAT, so that the carrier recombination of the Ni-CAT is inhibited, more electrons on the Ni-CAT are subjected to oxygen reduction reaction, and more holes are left on the CN and can be used for water oxidation reaction.
However, at present, most of conventional MOF materials are adopted as carriers, and other semiconductor materials are compounded to form the photocatalyst, so that the catalytic performance and stability of the photocatalyst are still required to be further enhanced.
Disclosure of Invention
The invention aims at: in order to solve the problem of poor activity of a photocatalyst formed by adopting MOF materials as carriers and compounding other semiconductor materials in the prior art, the preparation method of the photocatalyst for removing heavy metals in sewage is provided.
In order to achieve the above object, the present invention provides a method for preparing a photocatalyst for removing heavy metals from sewage, comprising the steps of:
s1: adding bismuth salt and metal salt into the solvent A, regulating the pH value to 2-10, and fully stirring and dissolving to form bismuth-based multi-metal oxide precursor solution;
s2: putting the bismuth-based multi-metal oxide precursor solution into a high-pressure reaction kettle, performing hydrothermal reaction for 6-48h at 120-200 ℃, filtering, and then cleaning and drying to obtain the bismuth-based multi-metal oxide;
s3: adding a metal source, an organic ligand and an additive into the solvent B, and fully stirring and dissolving to form a conductive MOF precursor solution;
s4: and (2) adding the bismuth-based multi-metal oxide prepared in the step (S2) into the conductive MOF precursor solution, stirring to enable the bismuth-based multi-metal oxide to be fully dissolved, then reacting for 2-48h at 25-150 ℃, filtering, cleaning and drying to obtain the bismuth-based multi-metal oxide/conductive MOF composite photocatalyst.
For further description of the above technical solution:
the bismuth salt in the step S1 is any one or a combination of at least two of hydrochloride, sulfate, nitrate or sodium bismuthate of bismuth.
For further description of the above technical solution:
the metal salt in the step S1 is any one or a combination of at least two of sodium molybdate, ammonium molybdate, sodium tungstate, ammonium tungstate, sodium orthovanadate, ammonium metavanadate or sodium metavanadate.
As a further description of the above technical solution:
the solvent A in the step S1 is any one or a combination of at least two of water, ethanol, glycol, glycerol and mannitol.
As a further description of the above technical solution:
the molar ratio of bismuth salt, metal salt and solvent A in the step S1 is 2:1:20-200.
As a further description of the above technical solution:
the metal source in the step S3 is any one or a combination of at least two of hydrochloride, nitrate, sulfate and acetate of iron, cobalt, nickel, copper, manganese and zirconium.
As a further description of the above technical solution:
the organic ligand in the step S3 is any one or a combination of at least two of hexaaminobenzene, 2,3,6,7,10, 11-hexaiminotriphenyl, 2,3,6,7,10, 11-hexahydroxytriphenyl, 1,2,4, 5-benzene tetramine, benzene hexathiol, 5,10,15, 20-tetra (4-carboxyphenyl) porphyrin, 1, 4-benzene dipyrazole ester, 2,3,9,10,16,17,23, 24-octaamino copper phthalocyanine or 1,3, 5-tri (4-carboxyphenyl) benzene.
As a further description of the above technical solution:
the solvent B in the step S3 is any one or a combination of at least two of dimethyl sulfoxide, N-dimethylformamide or water, and the mass ratio of the metal source to the solvent B is 1:50-200.
As a further description of the above technical solution:
the metal source in the step S3: the molar ratio of the organic ligand is 10:1-1:10.
As a further description of the above technical solution:
the mass ratio of the bismuth-based multi-metal oxide to the conductive MOF in the step S4 is 0.1:1-10:1.
In summary, due to the adoption of the technical scheme, the beneficial effects of the invention are as follows: the bismuth-based multi-metal oxide/conductive MOF composite material integrates the characteristics of high specific surface area, high porosity, high conductivity and high stability of the conductive MOF, can adjust the band gap width of the bismuth-based multi-metal oxide, is beneficial to improving the separation efficiency of photo-generated electrons/holes, and achieves the purpose of enhancing the photocatalysis efficiency.
Detailed Description
Exemplary embodiments of the present disclosure will be described in more detail below. While exemplary embodiments of the present disclosure are shown, it should be understood that the present disclosure may be embodied in various forms and should not be limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the disclosure to those skilled in the art.
Embodiment one:
1.0mmol of bismuth nitrate and 0.5mmol of ammonium molybdate are weighed and added into 40ml of ethanol, and fully stirred and dissolved to form bismuth molybdate (Bi) 2 MoO 6 ) Is a precursor solution of (a); in a high-pressure reaction kettle, reacting for 24 hours at 160 ℃, cleaning and drying to obtain Bi 2 MoO 6 The method comprises the steps of carrying out a first treatment on the surface of the 1.0mmol of cobalt acetate tetrahydrate and 6.0mmol of 2,3,6,7,10, 11-hexahydroxytriphenyl are weighed and added into 50ml of mixed solution of N, N-dimethylformamide/water (volume ratio is 1:4), and fully stirred and dissolved to form precursor solution of conductive Co-MOF; adding 0.2g Bi to the above solution 2 MoO 6 Stirring to fully disperse the materials; reacting for 18h at 110 ℃, cleaning and drying to obtain Bi 2 MoO 6 Conductive Co-MOF composite catalyst.
Embodiment two:
weighing 1.0mmol of bismuth sulfate and 0.5mmol of sodium tungstate, adding into 50ml of ethanol/glycol mixed solution (volume ratio of 4:1), stirring thoroughly to dissolve to form bismuth tungstate (Bi) 2 WO 6 ) Is a precursor solution of (a); in a high-pressure reaction kettle, reacting for 12 hours at 180 ℃, cleaning and drying to obtain Bi 2 WO 6 The method comprises the steps of carrying out a first treatment on the surface of the 1.0mmol of nickel chloride hexahydrate and 1.0mmol of 1,2,4, 5-benzene tetramine are weighed and added into 120ml of deionized water, and fully stirred and dissolved to form precursor solution of conductive Ni-MOF; adding 0.5. 0.5gBi to the above solution 2 WO 6 Stirring to fully disperse the materials; reacting for 2h at 60 ℃, cleaning and drying to obtain Bi 2 WO 6 Conductive Ni-MOF composite catalyst.
Embodiment III:
1.0mmol of bismuth sulfate and 0.5mmol of sodium orthovanadate are weighed and added into 100ml of deionized water, and fully stirred and dissolved to form bismuth vanadate (BiVO 4 ) Is a precursor solution of (a); in a high-pressure reaction kettle, reacting for 6 hours at 200 ℃, cleaning and drying to obtain BiVO 4 The method comprises the steps of carrying out a first treatment on the surface of the Weighing 1.0mmol of manganese nitrate hexahydrate and 1.0mmol of hexaaminobenzene, adding the manganese nitrate hexahydrate and the 1.0mmol of hexaaminobenzene into 60ml of dimethyl sulfoxide, adding 3ml of concentrated ammonia water, and fully stirring and dissolving to form a precursor solution of conductive Mn-MOF; adding the above solution to the above obtained 0.1g BiVO 4 Stirring to fully disperse, reacting at 60 ℃ for 2 hours, cleaning and drying to obtain BiVO 4 Conductive Mn-MOF composite catalyst.
Comparative example one:
1.0mmol of bismuth nitrate and 0.5mmol of ammonium molybdate are weighed and added into 40ml of ethanol, and fully stirred and dissolved to form bismuth molybdate (Bi) 2 MoO 6 ) Is a precursor solution of (a); in a high-pressure reaction kettle, reacting for 24 hours at 160 ℃, cleaning and drying to obtain Bi 2 MoO 6 。
Comparative example two:
1.0mmol of cobalt acetate tetrahydrate and 6.0mmol of 2,3,6,7,10, 11-hexahydroxytriphenyl are weighed and added into 50ml of mixed solution of N, N-dimethylformamide/water (volume ratio is 1:4), and fully stirred and dissolved to form precursor solution of conductive Co-MOF; the solution is reacted for 18 hours at 110 ℃, washed and dried to obtain the conductive Co-MOF.
The photocatalytic material is used for verifying the photocatalytic purification performance of Cr (VI) containing sewage by a photocatalytic reactor, and the photocatalytic purification performance is specifically as follows:
the catalytic effect of the catalyst was determined by comparing the amounts of Cr (VI) before and after the reaction, wherein the Cr (VI) removal rate (%) = (Cr (VI) before-Cr (VI) after-Cr (VI) before-x 100. The photocatalytic purification effect of Cr (VI) after the photocatalytic reaction is shown in table 1.
Table 1 shows the photocatalytic purification performance of Cr (VI) containing wastewater by the catalysts prepared in the examples and the comparative examples.
As can be seen from table 1, under the same reaction conditions, the removal efficiency of the bismuth-based multi-metal oxide/conductive MOF composite photocatalyst for Cr (VI) is significantly higher than that of the bismuth-based multi-metal oxide alone and the conductive MOF alone, and the catalytic efficiency of the bismuth-based multi-metal oxide/conductive MOF composite photocatalyst after being recycled for 6 times is also not much reduced, so that the catalytic efficiency of the bismuth-based multi-metal oxide/conductive MOF composite photocatalyst after being reused is also very high.
According to the invention, the bismuth-based multi-metal oxide and the conductive MOF are compounded to form the bismuth-based multi-metal oxide/conductive MOF composite material, so that the characteristics of high specific surface area, high porosity, high conductivity and high stability of the conductive MOF are integrated, and meanwhile, the band gap width of the bismuth-based multi-metal oxide can be adjusted, thereby being beneficial to improving the separation efficiency of photo-generated electrons/holes and achieving the purpose of enhancing the photocatalysis efficiency.
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should make equivalent substitutions or modifications according to the technical scheme of the present invention and the inventive concept thereof, and should be covered by the scope of the present invention.
Claims (7)
1. The preparation method of the photocatalyst for removing heavy metals in sewage is characterized by comprising the following steps of:
s1: adding bismuth salt and metal salt into a solvent A, regulating the pH value to be 2-10, fully stirring and dissolving to form bismuth-based multi-metal oxide precursor solution, wherein the solvent A is any one or a combination of at least two of water, ethanol, glycol, glycerol and mannitol;
s2: putting the bismuth-based multi-metal oxide precursor solution into a high-pressure reaction kettle, performing hydrothermal reaction for 6-48h at 120-200 ℃, filtering, and then cleaning and drying to obtain the bismuth-based multi-metal oxide;
s3: adding a metal source, an organic ligand and an additive into a solvent B, fully stirring and dissolving to form a conductive MOF precursor solution, wherein the organic ligand is any one or a combination of at least two of hexaaminobenzene, 2,3,6,7,10, 11-hexaiminotriphenyl, 2,3,6,7,10, 11-hexahydroxytriphenyl, 1,2,4, 5-benzene tetramine, benzene hexathiol, 5,10,15, 20-tetra (4-carboxyphenyl) porphyrin, 1, 4-benzene bipyrazole ester, 2,3,9,10,16,17,23,24-octaamino copper phthalocyanine or 1,3, 5-tri (4-carboxyphenyl) benzene, and the solvent B is any one or a combination of at least two of dimethyl sulfoxide, N-dimethylformamide or water, and the mass ratio of the metal source to the solvent B is 1:50-200 parts;
s4: and (2) adding the bismuth-based multi-metal oxide prepared in the step (S2) into the conductive MOF precursor solution, stirring to enable the bismuth-based multi-metal oxide to be fully dissolved, then reacting for 2-48h at 25-150 ℃, filtering, cleaning and drying to obtain the bismuth-based multi-metal oxide/conductive MOF composite photocatalyst.
2. The method for preparing a photocatalyst for removing heavy metals from sewage according to claim 1, wherein the bismuth salt in the step S1 is any one or a combination of at least two of bismuth hydrochloride, sulfate, nitrate or sodium bismuthate.
3. The method for preparing a photocatalyst for removing heavy metals from sewage according to claim 1, wherein the metal salt in the step S1 is any one or a combination of at least two of sodium molybdate, ammonium molybdate, sodium tungstate, ammonium tungstate, sodium orthovanadate, ammonium metavanadate or sodium metavanadate.
4. The method for preparing the photocatalyst for removing heavy metals from sewage according to claim 1, wherein the molar ratio of bismuth salt, metal salt and solvent a in the step S1 is 2:1:20 to 200.
5. The method for preparing a photocatalyst for removing heavy metals from sewage according to claim 1, wherein the metal source in the step S3 is any one or a combination of at least two of iron, cobalt, nickel, copper, manganese, zirconium hydrochloride, nitrate, sulfate, acetate.
6. The method for preparing a photocatalyst for removing heavy metals from sewage according to claim 1, wherein the metal source in step S3: the molar ratio of the organic ligand is 10:1 to 1:10.
7. the method for preparing a photocatalyst for removing heavy metals from sewage according to claim 1, wherein the mass ratio of bismuth-based multi-metal oxide to conductive MOF in the step S4 is 0.1:1-10:1.
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